JPS6316408B2 - - Google Patents
Info
- Publication number
- JPS6316408B2 JPS6316408B2 JP5354384A JP5354384A JPS6316408B2 JP S6316408 B2 JPS6316408 B2 JP S6316408B2 JP 5354384 A JP5354384 A JP 5354384A JP 5354384 A JP5354384 A JP 5354384A JP S6316408 B2 JPS6316408 B2 JP S6316408B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- epoxy resin
- reaction
- catalyst
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000007033 dehydrochlorination reaction Methods 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 10
- 235000013824 polyphenols Nutrition 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- -1 phenol compound Chemical class 0.000 description 5
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 5
- 229960001553 phloroglucinol Drugs 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WORJRXHJTUTINR-UHFFFAOYSA-N 1,4-dioxane;hydron;chloride Chemical compound Cl.C1COCCO1 WORJRXHJTUTINR-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RUUHDEGJEGHQKL-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)C RUUHDEGJEGHQKL-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、多官能エポキシ樹脂を高純度、高収
率で得るための新規な製造方法に関するものであ
る。本発明の製造方法は特に３官能以上の多官能
エポキシ樹脂に有用であり本発明の実施により得
られる多官能エポキシ樹脂は、耐熱性、耐水性に
すぐれた硬化物を与える。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel manufacturing method for obtaining a polyfunctional epoxy resin with high purity and high yield. The production method of the present invention is particularly useful for polyfunctional epoxy resins having trifunctionality or more, and the polyfunctional epoxy resin obtained by carrying out the present invention provides a cured product with excellent heat resistance and water resistance.
従来よりエポキシ樹脂はその優れた機械的特性
電気的特性、接着性、耐熱性により、接着剤、塗
料、電子部品用封止剤、カーボン繊維強化プラス
チツク用マトリツクス樹脂等広範囲に使用されて
いる。なかでもカーボン繊維強化プラスチツク用
マトリツクス樹脂としては主に耐熱性の点から、
フエノールノボラツクのポリグリシジルエーテル
やテトラグリシジルジアミノジフエニルメタン等
の多官能エポキシ樹脂が多用されている。
Epoxy resins have been used in a wide range of applications such as adhesives, paints, sealants for electronic parts, and matrix resins for carbon fiber-reinforced plastics due to their excellent mechanical properties, electrical properties, adhesive properties, and heat resistance. Among these, matrix resins for carbon fiber reinforced plastics are mainly used from the viewpoint of heat resistance.
Polyfunctional epoxy resins such as polyglycidyl ether of phenol novolak and tetraglycidyldiaminodiphenylmethane are often used.
エポキシ樹脂の製造方法は大きく分けて一段法
と二段法の２つが良く知られている。すなわちポ
リグリシジルエーテルの製造法を例にとつた場
合、前者は多価フエノール化合物をフエノール性
水酸基１当量に対し、３〜７モルの過剰量のエピ
クロルヒドリンに溶かし、次にフエノール性水酸
基１当量に対し、0.9〜1.2モルの水酸化ナトリウ
ム水溶液を滴下し、エピクロルヒドリンの付加反
応と脱HCl反応とを同時進行で行なわせてエポキ
シ樹脂を製造する方法である。これに対し後者
は、付加反応と脱塩化水素反応を２つの工程に分
けて行なうもので、まず原料の多価フエノール化
合物をフエノール性水酸基１当量に対し３〜７モ
ルの過剰のエピクロルヒドリンに溶かし、これ
に、アンモニウムクロリドの如き四級アンモニウ
ム塩を触媒として加え、付加反応を進行させる。
こうして生成したクロルヒドリンエーテルに対し
原料のフエノール化合物のフエノール性水酸基１
当量当り0.8〜1.2モルの水酸化ナトリウム水溶液
を滴下し、脱塩化水素反応を行つてエポキシ樹脂
を製造する方法である。より高度の特性、特に耐
熱性、耐水性を要求されるような用途に使用する
場合、エポキシ樹脂は高品質である必要があり、
両者を比較した場合、特に高純度、低塩素含有率
のエポキシ樹脂が得られるという点で後者の二段
法が優れているということは公知である。しかし
二段法を用いた場合でも３官能以上の多官能エポ
キシ樹脂を製造する場合、収率や純度が低下し特
に純度低下による耐熱性の低下が問題となつてい
る。 There are two well-known methods for producing epoxy resins: a one-stage method and a two-stage method. In other words, taking the method for producing polyglycidyl ether as an example, the former method involves dissolving a polyhydric phenol compound in an excess amount of epichlorohydrin of 3 to 7 moles per equivalent of phenolic hydroxyl group, and then dissolving the polyhydric phenol compound per equivalent of phenolic hydroxyl group. This is a method for producing an epoxy resin by dropping an aqueous solution of 0.9 to 1.2 mol of sodium hydroxide to simultaneously perform an epichlorohydrin addition reaction and an HCl removal reaction. On the other hand, in the latter method, the addition reaction and the dehydrochlorination reaction are carried out in two steps: first, the raw material polyphenol compound is dissolved in an excess of 3 to 7 moles of epichlorohydrin per equivalent of phenolic hydroxyl group; A quaternary ammonium salt such as ammonium chloride is added thereto as a catalyst to allow the addition reaction to proceed.
The phenolic hydroxyl group of the phenolic compound as the raw material for the chlorohydrin ether produced in this way
In this method, 0.8 to 1.2 moles of sodium hydroxide aqueous solution per equivalent is added dropwise to perform a dehydrochlorination reaction to produce an epoxy resin. When used in applications that require higher properties, especially heat resistance and water resistance, epoxy resins must be of high quality.
When comparing the two methods, it is known that the latter two-step method is superior in that an epoxy resin with particularly high purity and low chlorine content can be obtained. However, even when a two-stage method is used to produce a trifunctional or higher-functional epoxy resin, the yield and purity decrease, and in particular, a decrease in heat resistance due to the decrease in purity poses a problem.
そこで本発明者等はかかる従来技術の欠点に鑑
み、さらに高純度のエポキシ樹脂を高収率で製造
する方法について鋭意検討の結果、本発明を見い
出すに到つたのである。
In view of the shortcomings of the prior art, the inventors of the present invention have conducted extensive studies on a method for producing a highly purified epoxy resin at a high yield, and as a result, they have discovered the present invention.
即ち、本発明は次のからの３つの工程を経
てエポキシ樹脂を製造する方法に関する。
That is, the present invention relates to a method for producing an epoxy resin through the following three steps.
(1) 少くとも下記からの工程から成り立つこ
とを特徴とする多官能エポキシ樹脂の製造法。(1) A method for producing a polyfunctional epoxy resin characterized by comprising at least the following steps.
多価フエノール類に触媒の存在下で一般式
(A)で示されるところのエピハロヒドリン化合
物を付加される工程
Ｘ：Br又はCl
Ｒ：Ｈ又はCH3
上記の工程で得られた反応液を水で洗い
触媒を除去する工程
上記の工程で得られた反応物にアルカリ
化合物を加えて脱塩化水素反応を行い、目的
のエポキシ樹脂を得る工程
本発明の最も特徴ある点は、脱塩化水素反応工
程の前に、の水洗による脱触媒工程を入れたと
ころにある。他の工程は、従来の二段法とほぼ同
一であるが、後述するようにこの工程を入れた
ことによる収率、純度の向上効果はきわめて大き
なものである。脱触媒についてどのような機構で
純度、収率向上をもたらすかについては必ずしも
明らかではないが、おそらくエポキシ基の開環能
力をもつ触媒がエポキシ樹脂製造工程の最終段階
まで存在すると、生成したエポキシ樹脂同士が反
応してしまつて高分子量化したり、水とエピクロ
ルヒドリンの反応などの副反応が促進される可能
性があり、脱触媒によつてそれらの反応を抑制す
るため、高純度、高収率をもたらすものと思われ
る。 General formula of polyhydric phenols in the presence of a catalyst
The step of adding an epihalohydrin compound as shown in (A) X: Br or Cl R: H or CH 3 Step of washing the reaction solution obtained in the above step with water to remove the catalyst Adding an alkali compound to the reaction product obtained in the above step to perform a dehydrochlorination reaction , Step of Obtaining the Target Epoxy Resin The most distinctive feature of the present invention is that a decatalyst step by washing with water is included before the dehydrochlorination reaction step. The other steps are almost the same as the conventional two-stage method, but as will be described later, the addition of this step has a very large effect on improving yield and purity. It is not necessarily clear what mechanism of decatalyst brings about improvements in purity and yield, but it is likely that if a catalyst capable of ring-opening epoxy groups is present until the final stage of the epoxy resin manufacturing process, the resulting epoxy resin will be There is a possibility that the molecules may react with each other, resulting in a high molecular weight, or that side reactions such as the reaction between water and epichlorohydrin may be promoted. It seems that it will bring.
次に各工程における操作について詳細に述べ
る。 Next, the operations in each step will be described in detail.
においては、まず原料の多価フエノール化合
物をそのフエノール性水酸基１当量に対し３〜７
モルの過剰量の一般式(A)で示されるところのエピ
ハロヒドリン化合物に溶解し、触媒を加える。 First, the raw material polyphenol compound is added in an amount of 3 to 7 per equivalent of its phenolic hydroxyl group.
Dissolve in a molar excess of the epihalohydrin compound of general formula (A) and add the catalyst.
Ｘ：Cl・Br
Ｒ：Ｈ又はCH3
ここで使用される触媒としては、ベンジルトリ
メチルアンモニウムクロリド、テトラメチルアン
モニウムクロリド、テトラメチルアンモニウムブ
ロミド、トリエチルメチルアンモニウムクロリ
ド、β−ヒドロキシプロピルトリメチルアンモニ
ウムクロリド、ベンジルトリメチルアンモニウム
ブロミド等が挙げられる。触媒の使用量は原料の
多価フエノール化合物に対し、0.1〜10モル％で
ある。反応は、20〜180℃好ましくは50〜120℃の
温度で２〜40時間、実質的に無水の状態で行な
う。 X: Cl・Br R: H or CH 3 Catalysts used here include benzyltrimethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, triethylmethylammonium chloride, β-hydroxypropyltrimethylammonium chloride, benzyltrimethyl Examples include ammonium bromide. The amount of the catalyst used is 0.1 to 10 mol% based on the raw material polyhydric phenol compound. The reaction is carried out in substantially anhydrous conditions at a temperature of 20-180°C, preferably 50-120°C, for 2-40 hours.
においては、触媒は水に易溶のため、反応液
に水を注ぐだけで容易に触媒のみを除くことがで
き、しかも水とエピクロルヒドリンは混和しない
ため水の除去も容易である。水洗は１回でも良い
が充分な効果をあげるためには３回程行なうの
が、望ましい。 Since the catalyst is easily soluble in water, only the catalyst can be easily removed by simply pouring water into the reaction solution.Moreover, since water and epichlorohydrin are immiscible, water can also be easily removed. Washing with water may be done once, but it is preferable to wash with water three times in order to obtain a sufficient effect.
においては、で得られたクロルヒドリンエ
ーテルを、原料のフエノール化合物のフエノール
性水酸基１当量当り、0.8〜1.2モルのアルカリ化
合物を加えることによつて脱塩化水素反応を行な
い目的のエポキシ樹脂を得る。ここで使用される
アルカリ化合物は、水酸化カリウム、水酸化ナト
リウム、ナトリウムメチラートなどが知られてお
りいずれも使用可能である。 In this step, the chlorohydrin ether obtained in step 1 is subjected to a dehydrochlorination reaction by adding 0.8 to 1.2 moles of an alkali compound per equivalent of the phenolic hydroxyl group of the phenolic compound as the raw material to obtain the desired epoxy resin. . As the alkali compound used here, potassium hydroxide, sodium hydroxide, sodium methylate, etc. are known, and any of them can be used.
〔本発明の効果〕
本発明によれば、耐熱性、耐水性に優れた多官
能エポキシ樹脂を高純度かつ高収率で得ることが
できる。[Effects of the Present Invention] According to the present invention, a polyfunctional epoxy resin having excellent heat resistance and water resistance can be obtained with high purity and high yield.
以下、実施例により本発明を更に詳細に説明す
る。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
撹拌装置、温度計、滴下ロート、エピクロルヒ
ドリンと水の共沸蒸気を冷却液化し、エピクロル
ヒドリン層だけを反応系に戻す装置のついた500
mlの四ツ口フラスコに、フロログルシン（(B)式で
示されるフエノール性水酸基を３個もち結晶水が
２分子ついているフエノール化合物）24.3ｇ
（0.15mol）、エピクロルヒドリン177.2ml
（2.25mol）を入れ、オイルバス中で50℃で加熱
撹拌し、フロログルシンを完全に溶解させた。Example 1 500 with a stirring device, a thermometer, a dropping funnel, and a device to cool and liquefy the azeotropic vapor of epichlorohydrin and water and return only the epichlorohydrin layer to the reaction system.
24.3 g of phloroglucin (a phenolic compound represented by formula (B) that has three phenolic hydroxyl groups and two molecules of water of crystallization) in a ml four-necked flask.
(0.15mol), epichlorohydrin 177.2ml
(2.25 mol) was heated and stirred in an oil bath at 50°C to completely dissolve phloroglucin.
均一の溶液になつたら反応糸を100mmHg程度の
減圧にして、結晶水とエピクロルヒドリンを共沸
させ水分を除去した後、常圧にもどしベンジルト
リメチルアンモニウムクロリド1.67ｇ
（0.009mol）を加え50℃で24hr撹拌した。その
後、精製水200mlを加え、10分間激しく撹拌した
後静置し２層に分離し水槽部分を吸引除去する操
作を３回行ない触媒であるベンジルトリメチルア
ンモニウムクロリドを除いた。そして再び減圧加
熱し、系内に残つた微量の水分を共沸除去した後
水酸化ナトリウム36％水溶液50ｇを3hrかけて滴
下した。その際反応系は温度80℃、100mmHgの減
圧に保持し水分を共沸で系外に除去し続けた。滴
下終了後、そのままの状態で30分間撹拌を続けた
後、過剰のエピクロルヒドリンを蒸留で除いた。
そしてメチルイソブチルケトン100ml、水100mlを
加え生成した塩を分離した後くり返し３回水洗し
有機層を取り出し、エバポレーターで溶媒を除去
しフロログルシントリグリシジルエーテルを得
た。最終的な収量は、43ｇでありこれは理論収量
の98％という高収率であつた。塩酸−ジオキサン
法によつてエポキシ当量を測定した結果、135で
あり、GPC分析の結果、２量体以上のオリゴマ
ー含有量は10％であることがわかつた。 Once a homogeneous solution is obtained, reduce the pressure of the reaction thread to about 100 mmHg, azeotrope the water of crystallization and epichlorohydrin to remove water, then return to normal pressure and add 1.67 g of benzyltrimethylammonium chloride.
(0.009 mol) was added and stirred at 50°C for 24 hours. Thereafter, 200 ml of purified water was added, stirred vigorously for 10 minutes, left to stand, separated into two layers, and the water tank portion was removed by suction three times to remove the catalyst, benzyltrimethylammonium chloride. Then, the system was heated under reduced pressure again to azeotropically remove a small amount of water remaining in the system, and then 50 g of a 36% aqueous solution of sodium hydroxide was added dropwise over 3 hours. At this time, the reaction system was maintained at a temperature of 80°C and a reduced pressure of 100 mmHg, and water was continuously removed from the system by azeotropy. After the dropwise addition was completed, stirring was continued for 30 minutes, and then excess epichlorohydrin was removed by distillation.
Then, 100 ml of methyl isobutyl ketone and 100 ml of water were added, and the resulting salt was separated, washed repeatedly with water three times, the organic layer was taken out, and the solvent was removed using an evaporator to obtain phloroglucin triglycidyl ether. The final yield was 43 g, which was a high yield of 98% of the theoretical yield. The epoxy equivalent was measured by the hydrochloric acid-dioxane method and found to be 135, and the GPC analysis revealed that the content of dimers and higher oligomers was 10%.
比較例１、実施例１と同様な装置を用いフロロ
グルシンとエピクロルヒドンも同量仕込み結晶水
を除去する工程まで同様の操作を行なつた後、す
ぐに水酸化ナトリウム水溶液を滴下し、一段法に
よる合成法を試みたところ、滴下中に、不溶のゲ
ル状物が多量に発生し製造不可能であつた。 Using the same equipment as in Comparative Example 1 and Example 1, the same amounts of phloroglucin and epichlorohydone were charged, and the same operations were carried out up to the step of removing crystallization water. Immediately, an aqueous sodium hydroxide solution was added dropwise to synthesize the one-step method. When this method was tried, a large amount of insoluble gel-like material was generated during the dropping process, making it impossible to produce the product.
比較例２、実施例１における水洗による触媒除
去の工程を行なわなかつた以外は全く同じ操作を
行ないフロログルシントリグリシジルエーテルを
得た。最終的な収量は38ｇで、収率は86％であつ
た。塩酸−ジオキサン法によつて測定した結果エ
ポキシ当量は152であつた。又GPC分析の結果、
２量体以上のオリゴマーは18％含まれることがわ
かつた。 Phloroglucin triglycidyl ether was obtained by carrying out exactly the same operation as in Comparative Example 2 and Example 1, except that the step of removing the catalyst by washing with water was not performed. The final yield was 38g, giving a yield of 86%. The epoxy equivalent was 152 as measured by the hydrochloric acid-dioxane method. Also, as a result of GPC analysis,
It was found that 18% of the oligomers were dimers or higher.
Claims (1)
とを特徴とする多官能エポキシ樹脂の製造法。 多価フエノール類に触媒の存在下で一般式(A)
で示されるところのエピハロヒドリン化合物を
付加させる工程 Ｘ：Br又はCl Ｒ：Ｈ又はCH3 上記の工程で得られた反応液を水で洗い触
媒を除去する工程 上記の工程で得られた反応物にアルカリ化
合物を加えて脱塩化水素反応を行い、目的のエ
ポキシ樹脂を得る工程[Scope of Claims] 1. A method for producing a polyfunctional epoxy resin, characterized by comprising at least the following steps. General formula (A) in the presence of a catalyst to polyhydric phenols
The step of adding an epihalohydrin compound as shown in X: Br or Cl R: H or CH 3 Process of washing the reaction solution obtained in the above step with water to remove the catalyst Adding an alkali compound to the reaction product obtained in the above step to perform a dehydrochlorination reaction , the process of obtaining the desired epoxy resin
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5354384A JPS60199018A (en) | 1984-03-22 | 1984-03-22 | Production of epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5354384A JPS60199018A (en) | 1984-03-22 | 1984-03-22 | Production of epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60199018A JPS60199018A (en) | 1985-10-08 |
| JPS6316408B2 true JPS6316408B2 (en) | 1988-04-08 |
Family
ID=12945712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5354384A Granted JPS60199018A (en) | 1984-03-22 | 1984-03-22 | Production of epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60199018A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101263324B1 (en) | 2010-05-06 | 2013-05-15 | 한국생산기술연구원 | Method for Preparing Phloroglucinol Epoxy Laminated Body |
| JP6590126B2 (en) * | 2017-07-21 | 2019-10-16 | Dic株式会社 | Epoxy resin, epoxy resin composition containing the same, and cured product using the epoxy resin composition |
-
1984
- 1984-03-22 JP JP5354384A patent/JPS60199018A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60199018A (en) | 1985-10-08 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |